KR20100083171A - Water storage tank - Google Patents

Abstract

The present invention relates to a storage tank loaded with an aqueous medium and made of porous, freely flowing particles, wherein the particles are formed from a hydrophobic polymer and the loading of said particles contains at least one particular mediator additive of the general formula, the use of which as an entrainer delivery agent for removing volatile components from plastics, for evenly doping intermediate plastic products and/or plastic articles with adjuvants as a soil improvement agent such as a delivery agent for a pest management agent or fertilizer.

Description

Water storage tank

The present invention is filled with an aqueous fluid and consists of a reservoir of porous free-flowing particles, wherein the particles are preferably formed from a hydrophobic polymer, the filler comprising one or more compatibilizers of formula (I) and entraining agents for the removal of volatile components, in particular odor-producing aids from the plastic, or for the uniform addition of plastic aids or as a water reservoir or soil It relates to the use of said charged reservoir as a improver.

It is well known that aqueous fluids, in particular water, can be used as entraining agents in order to achieve a reduction in residual monomer content, especially when processing polymers. This method can also achieve a reduction in the release of volatile organics that can release odors, which is inevitable when processing recycled polymers.

In order to achieve maximum efficiency when water is introduced into the polymer to be treated, porous particles filled with water can be incorporated into the polymer melt during thermoplastic processing of the polymer. Water is discharged during the extrusion process, acting as entrainer for volatiles, which are removed together with water vapor.

The porous particles used here are preferably made of hydrophobic polymers such as polyethylene or polypropylene. Their characteristics are, in particular, high chemical stability and high mechanical and thermal stability. Thus, these polymers are also suitable for the production of porous particles that can be filled with an aqueous fluid and passed forward for further use.

WO 2005/003215 describes porous, at least somewhat open pores, each corresponding to a reservoir filled with an aqueous fluid. However, a disadvantage of this type of particles or reservoirs is that the particles must be filled with a relatively large amount of surfactant before they are filled with water. This is the only way to achieve a fill level of at least 50% using aqueous fluids. However, the filling of particles with relatively large amounts of surfactants is problematic because these surfactants can exert considerable influence on the intended use of the fillers. In the case where filled reservoirs are used to deliver entraining agents, one possibility is that in particular surfactants form decomposition products, which firstly consume entraining agents, i.e. water, and secondly they themselves It can be an odor-generating substance.

It is therefore an object of the present invention to provide a reservoir having a high level of aqueous fluid fill, so that the entire fill of the reservoir can be used intact, ie essentially intact, for the desired use.

This object is achieved through the reservoir of the invention, which is filled with an aqueous fluid and consists of porous free-flowing particles, wherein the particles of the reservoir are preferably formed from hydrophobic polymers, and the average size of the particles is preferably 50 to 5000 μm, the particles preferably have at least some open pore structure, the average pore diameter of the particles is preferably 1 to 200 μm, and the aqueous filler of the reservoir comprises at least one compatibilizer of formula (I) Additives.

[Formula I]

In Formula I,

R ₁ is an alkyl moiety having 1 to 6 carbon atoms,

A and B are the same or different and are an alkyl moiety having 1 to 6 carbon atoms or a group of formula -ZR ₂ -R ₃ ,

Z is a residue of the formula -C ₁ H _2r -O-,

r is an integer of 1 to 10, preferably 1 to 4, particularly preferably 3,

R ₂ is a residue of the formula-(C ₂ H ₄ O-) _n (C ₃ H ₆ O-) _m ,

m is 0 or an integer from 1 to 4,

n is an integer of 1 to 12, and the arrangement of units repeated n times and m times each may be block or random,

R ₃ is an OH group or an alkyl residue having 1 to 6 carbon atoms, preferably a methyl residue,

x is 0 or an integer of 1 to 3,

y is 0 or an integer of 1 to 3,

In this case, the compatibilizer additive should always have at least one group of the formula -ZR ₂ -R ₃ .

The compatibilizer additive used preferably has an average molecular weight of the moiety of the formula-(C ₂ H ₄ O-) _n (C ₃ H ₆ O-) _{m in} the range from 100 to 5000, preferably from 150 to 1000 and particularly preferably Comprises a compound of formula (I) which is between 200 and 600.

R ₁ is a residue selected from the group consisting of methyl, ethyl, propyl, isopropyl and n-propyl, n, m, x, y, r, A, B, Z, R ₂ and R ₃ are It is likewise preferred that the compounds of formula (I), defined as such, are used as compatibilizer additives.

Other preferred compatibilizer additives include A being a methyl moiety or a group of formula -ZR ₂ -R ₃ , B is a methyl moiety, and R ₂ is a formula-(C ₂ H ₄ O-) _n or-(C ₂ H ₄ O -) a residue of _n (C ₃ H ₆ O-) _m, m is 1 or 2, n is 5, 6, 7, 8 or 9 and, x, y, r, Z and R ₃ are the above-mentioned As defined.

The compatibilizer additives presented for the preferred use should all contain at least one group of the formula -ZR ₂ -R ₃ , respectively.

The preparation of the compatibilizer additives set forth above is known to those skilled in the art. See US-A 3,299,112 or US-A 4,933,002 for corresponding techniques.

Porous, preferably hydrophobic particles used in the present invention for the production of filled reservoirs and having at least some open pore structure are sponge-like, cellular microstructures, or other network-like It has a network-like microstructure. The pores are at least somewhat open pores, and in at least some areas of the particle structure there is a connection between the pores present in the particles and the channel.

The particles used in the present invention are preferably composed of hydrophobic polymers such as thermoplastic polymers and / or elastomers. The particles used in the invention are polyolefins, in particular polymers selected from the group consisting of polyethylene or polypropylene, fluoro polymers, polycarbonates, polystyrenes, polyesters, polyvinyl chlorides, polyurethanes, polymethacrylates and polyamides, or It is especially preferable to consist of a mixture of these polymers.

Particles used in the present invention are HDPE (high density polyethylene), LDPE (low density polyethylene), LLDPE (linear low density polyethylene), UHMW PE (ultra high molecular weight polyethylene), mPE (metallocene PE), polypropylene, ethylene-propylene copolymer , Polyisobutene, PB (polybutylene), PMP (polymethylpentene), PTFE (polytetrafluoroethylene), FEP (perfluoroethylene-propylene copolymer), CTFE (polychlorotrifluoroethylene), ECTFE (ethylene-chlorotrifluoroethylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), tetrafluoroethylene-propylene copolymer, polyvinylidene fluoride, polyvinyl chloride, tetrafluoroethylene and hexa Copolymers of fluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers, copolymers of ethylene-tetrafluoroethylene, PC (polycarbonate), poly Styrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyamide (PA) (e.g. Particular preference is given to at least one polymer or copolymer selected from the group consisting of PA6).

The porosity of the particles used in the present invention is preferably at least 30% by volume, more preferably at least 50% by volume, particularly preferably at least 60% by volume. The porosity of the particles used in the present invention is particularly preferably 50 to 80% by volume. Porosity (volume basis) is measured by methods well known to those skilled in the art. By way of example, the porosity of the particles used in the present invention may be determined by a pycnometric test method using water as a non-wetting liquid or by a suitable intrusion method, for example, by mercury intrusion. It can be measured by.

The size of the particles used in the present invention is preferably 10 to 10000 μm, more preferably 200 to 7000 μm, even more preferably 500 to 5000 μm, most preferably 1000 to 4000 μm, especially 1500 to 3000 μm. to be. The mean particle size is preferably determined microscopically using representative specimen volume and micrometer lens systems or preferably using appropriate image evaluation methods. Measurements of this type are known to those skilled in the art.

In one preferred embodiment of the invention, the average pore diameter of the particles used in the invention is preferably from 0.5 to 500 μm, more preferably from 1 to 400 μm, even more preferably from 1 to 300 μm, most preferably It is 1-200 micrometers and especially 1-100 micrometers, This average pore diameter can be measured by a well-known measuring method. By way of example, the average pore size is determined based on digitalized scanning electron micrographs on the fractured surface of the specimen, and these are evaluated by appropriate image analysis software. The pore diameter of the pores of about 50 to 100 is measured here in μm from the scanning electron micrograph. The associated average pore diameter is calculated as the average of the individual values.

The particles presented above and used in the present invention are commercially available.

Surprisingly, it has been found that the aqueous fluid, in particular water, should contain only minor amounts of compatibilizer additives of formula (I) to ensure that the reservoir is filled with at least 30% by weight, based on the total amount of the reservoir filled. lost.

Thus, using an aqueous fluid, preferably in each case based on the total weight of the aqueous fluid, in order to achieve a water-fill level of preferably at least 30% by weight, based on the total amount of the reservoir filled Is at least 4% by weight, more preferably at most 3% by weight, even more preferably at most 1% by weight, most preferably at most 0.5% by weight and in particular at most 0.1% by weight of at least one compatibilizer additive of formula (I) It is sufficient to be present as a suspension or solution in an aqueous fluid provided for the charge.

The attainable filling level of the particles used in the present invention with an aqueous fluid, in particular water, is preferably up to at least 30% by weight, more preferably at least 50% by weight, in each case based on the total weight of the filled reservoir. Up to%, particularly preferably at least 60% by weight.

For this type of filling, in each case 0.01 to 5% by weight, more preferably 0.03 to 3% by weight, even more preferably 0.05 to 2% by weight, based on the total weight of the filled reservoir It is particularly useful that at least one compatibilizer additive of formula I is present in the packing of the reservoir, preferably in an amount of 0.05 to 1% by weight.

The filling of the particles used in the present invention by the aqueous fluid in the present invention is such that the particles are preferably at least 10 minutes, more preferably at least 30 minutes, with a compatibilizer additive of the formula (I), optionally with shaking and / or stirring. , Even more preferably at least 60 minutes, most preferably at least 70 minutes and in particular at least 90 minutes.

In order to speed up the wetting process, ultrasound may also be used and / or vacuum applied. Particles used in the present invention are particularly preferably contacted by such a stage with an aqueous fluid comprising a compatibilizer additive of formula (I).

The compatibilizer additives are present in the present invention in dispersed form, preferably in dissolved or suspended form.

It is particularly preferable that the wetting and filling of the particles used in the invention take place in one step, preferably under vacuum. Thus, less time is required for the complex wetting process, which results in time savings and cost savings.

The aqueous fluid used for the filling is preferably water.

The present invention also provides the use of the above described filled reservoir as a water reservoir.

The invention also relates to the delivery of entraining agents for the removal of volatile constituents (e.g. volatile organic compounds) and / or odor-releasing substances from plastics, in particular in the case of undesirable volatiles and in case of plastics (e. G. Thus, the delivery of entraining agents for the removal of odor-generating compounds and, accordingly, to reduce the release of said contaminants from the plastic items produced from the reclaimed material, or by the aid of plastic intermediates and / or plastic items. It provides the use of the filled reservoir described above for uniform doping.

For the addition of this form of auxiliaries into plastics, the filled aqueous fluid, together with the compatibilizer additive used in the present invention, is an antifogging agent, antioxidant, flame retardant, lubricant, light stabilizer, thermal stabilizer and other stabilizers. Auxiliary agents selected from the group consisting of agents, UV filters, mold release agents, antistatic agents, foaming agents, impact modifiers, dyes, fillers, optical brighteners and rheological additives.

The invention also relates to a reservoir filled with an aqueous fluid for soil improvement, irrigation, fertilization and / or plant protection, wherein the filling thereof is a function by use, such as fertilizers, plant-protecting agents or pesticides. And / or growth-promoters).

The invention also provides the use of the reservoir of the invention, preferably filled with water, for humidification and / or air-conditioning.

For all intended uses of the reservoir of the invention filled with an aqueous fluid, preferably water, it is useful for the filler to contain a biocide to prevent colonization by microorganisms during storage of the filled reservoir.

The invention also provides recycled plastics to the filled reservoirs of the present invention that deliver entraining agents to prevent or reduce the release of volatile organic compounds and / or odor-releasing materials from items produced from recycled plastics during processing of recycled plastics. Provide a way to handle it.

The following examples are used for further explanation of the invention, but do not limit the invention.

Example

Compatibilizer additives

The compounds of formula (I) shown in Table 1 below were used as compatibilizer additives.

Example  One

700 g of porous polypropylene (PP) particles having an average size of 3 mm x 3 mm, a porosity of 70% by volume and an average pore size of 20 to 80 μm were obtained using a tumbler mixer at a CA 1 concentration of 0.08% by weight. 1300 g of an aqueous solution of 1) (= 0.1 wt% compatibilizer additive, based on the total weight of the unfilled particles; = 0.06 wt% compatibilizer additive, based on the total weight of the filled reservoir). The filling time was 90 minutes, which gave a water absorption of 65% by weight based on the total weight of the filled reservoir.

Example  2 to 7

According to Example 1 (0.08% by weight aqueous solution), the other porous particles shown in Table 2 were charged. In each case, here the water filling (referred to as weight percent) is based on the total weight of the filled reservoir of the invention.

HDPE: high density polyethylene, PC: polycarbonate, PA6: nylon-6, PS: polystyrene, PET: polyethylene terephthalate, PP: polypropylene

* Based on the total weight of the filled reservoir.

Measurement of charge level and charge time for porous particles

A precondition for the measurement of the filling level and characteristic filling time is that the porosity by volume of the material to be investigated is known. About 10-30 g of material to be irradiated is weighed in a 500 ml glass flask. The amount of water to be added to the particles, ie the volume of water to be added, is determined from the porosity of the particles or from the pore volume of the amount of particles weighed in the flask, respectively. The pore volume of the particles here can be determined from the weight in the flask, the density ρ and the porosity ε of the polymer. In the first step, the amount of water metered for the material is such that complete absorption of water by the particles can be expected. For this purpose, the volume of water added corresponds to about 60% pore volume measured for the particles.

After the addition of water, the glass flask containing the particles is connected to a suitable mixing device, such as a rotary evaporator, using a water bath adjusted to 25 ° C. Then, the particles continue to dry until they dry externally and have good fluidity. A stopwatch is used to measure the filling time from the start of the mixing process to the complete absorption of water.

The glass flask is then removed from the mixing apparatus and an additional amount of water corresponding to 5% of the pore volume is added. The mixing is then repeated and again a stopwatch is used to determine the time required for complete absorption of this amount of water by the particles.

This process is repeated until the particles are saturated with water and the amount of water metered to the material corresponds to 5% of the pore volume each time. Here, saturation is defined as a state where water is still sensed on the glass flask wall and / or some caking of particles is detected, even after a full filling time of 3 hours. Here, the time taken as a characteristic filling time is the sum of the filling times measured with a stopwatch for each said period in which the respective amount of water has been completely absorbed by the particles. The saturated particles are then weighed again to find the difference from the initial weight to determine the total amount of water absorbed by the particles. The filling level of the particles is obtained from the ratio of the total amount of water absorbed by the particles to the weight of the particles not saturated with water (% by weight).

Example  8 - PP On the reproduction  For sensory examination

The polypropylene regeneration was 0.5 wt%, based on the total weight of the reservoir, as in Example 1, filled with an aqueous filler comprising CA 1 as a compatibilizer additive for delivery of entraining agents, respectively, The pellets were devolatilized and processed in an extruder at 200 ° C. using 1%, 1.5%, 2%, 2.5% or 3% by weight. Test specimens of each devolutylated pellets were stored according to their odor characteristics after storage according to VDA 270 "Bestimmung des Geruchsverhaltens von Werkstoffen der Kraftfahrzeuginnenausstattung" [Determination of odor characteristics of materials for internal trim of motor vehicles]. Was tested. The VDA 270 assay is an established method for measuring odor emission from plastics after storage under certain temperature and humidity conditions using test agents for evaluating odors; The evaluation scale here is performed from 1 to 6.

For the test, test specimen 0 which was not treated with entrainer and test specimens 1 to 6 treated with entrainer were prepared according to variant 3 of VDA 270 and had a odorless seal and cover. And stored at a temperature of 80 ± 2 ° C. for 2 hours ± 10 minutes in a glass vessel. In order to comply with the storage period of variant 3 of VDA 270, the test vessel containing the material was subsequently stored in an oven.

For the odor test, each specimen was evaluated by three test personnel after storage. Table 3 below provides the test results:

Addition amount of charged reservoir prepared as in Example 1 for delivery of entraining agent

Claims (18)

A reservoir filled with an aqueous fluid and composed of porous free-flowing particles,
The particles are preferably formed from a hydrophobic polymer and the aqueous filler comprises at least one compatibilizer additive of formula (I).
Formula I

In Formula I,
R ₁ is an alkyl moiety having 1 to 6 carbon atoms,
A and B are the same or different and are an alkyl moiety having 1 to 6 carbon atoms or a group of formula -ZR ₂ -R ₃ ,
Z is a residue of the formula -C ₁ H _2r -O-,
r is an integer of 1 to 10, preferably 1 to 4, particularly preferably 3,
R ₂ is a residue of the formula-(C ₂ H ₄ O-) _n (C ₃ H ₆ O-) _m ,
m is 0 or an integer from 1 to 4,
n is an integer of 1 to 12, and the arrangement of units repeated n times and m times each may be block or random,
R ₃ is an OH group or an alkyl moiety having 1 to 6 carbon atoms,
x is 0 or an integer of 1 to 3,
y is 0 or an integer of 1 to 3,
At this time, the compatibilizer additive always has one or more groups of the formula -ZR ₂ -R ₃ . The compound of claim 1, wherein R ₁ is a residue selected from the group consisting of methyl, ethyl, propyl, isopropyl and n-propyl, and n, m, x, y, r, A, B, Z, R ₂ and R Charged storage body, characterized in that ₃ is defined as claimed in claim 1. A compound according to claim 1 or 2, wherein A is a methyl moiety or a group of formula -ZR ₂ -R ₃ , B is a methyl moiety, and R ₂ is a formula-(C ₂ H ₄ O-) _n or-(C ₂ H ₄ O-) _n (C ₃ H ₆ O-) _m is a residue, m is 1 or 2, n is 5, 6, 7, 8 or 9, x, y, r, Z and R ₃ Wherein the is as defined in claim 1. 4. Charged according to claim 1, characterized in that the particles consist of polyolefins, preferably polyethylene or polypropylene, polycarbonates, fluoropolymers, polystyrenes, polyesters or polyamides. Storage body. 5. The filled reservoir according to claim 1, wherein the porosity of the particles is at least 30 vol%, preferably 50 to 80 vol%. 6. 6. The filled reservoir according to claim 1, wherein the average size of the particles is 10-10000 μm and the average pore diameter of the particles is 0.5-500 μm. 7. The filled reservoir according to claim 1, wherein the amount of the compatibilizer additive present is from 0.01 to 5% by weight, based on the total weight of the filled reservoir. The amount of filling of the reservoir with the aqueous fluid, preferably water, is 30% by weight or more, more preferably based on the total weight of the filled reservoir. Is at least 50% by weight, particularly preferably at least 60% by weight. The filled reservoir according to any one of claims 1 to 8, wherein the aqueous fluid is water. 10. Charged storage according to any one of the preceding claims, characterized in that the aqueous charge comprises up to 4% by weight of one or more compatibilizer additives, based on the total weight of the aqueous fluid. sieve. 10. Charged storage according to any one of the preceding claims, characterized in that the aqueous fluid charge comprises 0.1% by weight of one or more compatibilizer additives, based on the total weight of the aqueous fluid. sieve. The method of claim 1, wherein the aqueous fluid filler comprises one or more plant-protecting agents, pesticides or fertilizers, and / or any other growth-promoting agent, in combination with one or more of the compatibilizer additives. Charged storage body, characterized in that. The filled reservoir according to claim 1, wherein the aqueous fluid comprises one or more plastic auxiliaries, together with the compatibilizer additive. Use of a filled reservoir as claimed in any one of claims 1 to 11 as a water reservoir. To deliver entraining agents for the removal of volatile components from the plastic; To deliver entraining agents for the removal of volatile organic compounds and / or odor-releasing materials from plastics, in particular reclaimed materials; Use of a filled reservoir as claimed in any of claims 11 to 13 for the uniform addition of plastic aids. Use of a filled reservoir as claimed in claim 11 or 12 for soil improvement, irrigation, fertilization and / or plant protection. 15. Use of a filled reservoir according to claim 14 for humidification and / or air-conditioning. Release of volatile organic compounds and / or odor-releasing materials from plastic items produced from plastic recycles by adding the charged reservoir as claimed in any one of claims 1 to 11 and 14 during the manufacturing process. How to reduce or suppress